CN115957638A - Porous metal-based ceramic composite membrane and preparation method thereof - Google Patents
Porous metal-based ceramic composite membrane and preparation method thereof Download PDFInfo
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a porous metal-based ceramic composite membrane and a preparation method thereof, and relates to the field of ceramic composite membranes. The composite membrane comprises: the ceramic composite layer, the metal powder transition layer and the porous metal matrix; the metal powder transition layer is arranged between the ceramic composite layer and the porous metal matrix. The invention also provides a porous metal-based ceramic composite membrane and a preparation method thereof, the method prepares the slurry for the metal powder transition layer and the ceramic layer by the grinding and dispersing all-in-one machine, effectively solves the problem that the superfine metal and ceramic powder are easy to agglomerate in the slurry, and prepares the final composite porous membrane layer by sintering and forming after powdering at negative pressure to form a membrane layer with uniform thickness.
Description
Technical Field
The invention relates to the field of ceramic composite membranes, in particular to a porous metal-based ceramic composite membrane and a preparation method thereof.
Background
Nowadays, with the continuous development of science and technology, higher requirements are put forward on the performance of filter materials in the fields of biology, medicine, electronic equipment and the like, and miniaturization, high precision, high strength and strong corrosion resistance become the key research direction for the development of filter materials. In general, the filtering precision of the metal porous material is difficult to reach the nano level or the submicron level, and the gas-solid/liquid-solid separation under various harsh working conditions is difficult to meet, and the pore diameter of the ceramic membrane material can be nano level due to the special physical and chemical characteristics of the ceramic membrane material, so that the nano-scale filtering effect is realized. Therefore, in order to combine the advantages of high mechanical strength of the metal membrane and high separation precision of the ceramic membrane, a metal-ceramic composite membrane is provided, which is a composite material taking porous metal as a matrix and porous ceramic as a membrane layer. The metal-ceramic composite porous material has the advantages of metal processability, excellent sealing property and heat resistance and corrosion resistance of ceramic, improves the mechanical property and environmental compatibility of the material, and widens the application of the material in high-temperature corrosion and other harsh environments.
Common methods for preparing metal ceramic composites include anodic oxidation, magnetron sputtering, chemical vapor deposition, and sol-gel methods. The anodic oxidation method comprises the steps of placing a metal porous matrix in electrolyte to generate anodic oxidation reaction, generating an oxidation transition layer on the surface of the matrix, coating oxide powder on the transition layer, drying and sintering to obtain the metal ceramic composite filter membrane; the magnetron sputtering method belongs to one of physical vapor deposition, and target particles are sputtered and deposited on the surface of a substrate under the action of an electric field and a magnetic field to form a porous film-shaped structure; the chemical vapor deposition method is that a vapor compound containing target deposition elements and a porous substrate are subjected to chemical reaction under the condition of normal pressure or vacuum to generate solid substances such as oxide or nitride containing film elements, and the solid substances are deposited on the surface of the porous substrate to form a porous coating; the chemical vapor deposition is suitable for coating films on the surfaces or inner holes of parts with complex shapes, and is difficult to deposit on a certain surface, low in deposition efficiency and easy to generate defects. The sol-gel method is a relatively conventional method for preparing a metal ceramic composite material, and ceramic oxide sol is coated on the surface of a metal porous substrate, or the metal substrate is placed in the sol to form a film in a pulling mode, and then the film is dried and cured to form gel.
In the published patent No. cn201110393344.X, a preparation method of a metal-based ceramic composite filter membrane is provided, wherein a porous metal membrane layer is prepared on the surface of a porous metal matrix, and then is immersed into an electrolyte to carry out anodic oxidation to obtain a transition layer, and then oxide ceramic slurry is coated on the prepared transition layer, dried and sintered to obtain the porous ceramic filter membrane. The method can be used for preparing a ceramic membrane-coated metal porous material, but has certain limitation on the selection of the type of the base material, particularly the situation that a certain specific surface membrane layer is formed by a tubular membrane is difficult to realize, and the uniformity and consistency of the oxidation transition layer on the surface of the base material with a special structure type are difficult to ensure due to more control factors required by the electrolytic oxidation reaction. For example, patent cn201510097165.X "a method for preparing a porous oxide film on the surface of a metal carrier", which is disclosed in the specification, is to coat the surface of the metal carrier, which is cleaned and has surface oxide scale removed, with a mixed slurry of porous oxide and oxide sol to be prepared, dry the mixture, then perform heat-preservation sintering in a reducing atmosphere, improve the film-forming property by adding oxide powder into the oxide sol, and shorten the drying time of the film layer. The method is simple and easy to implement, the film forming efficiency is high, but the temperature resistance of the film layer is poor, the bonding strength with a matrix is relatively low, and the problems of cracking and falling easily occur at high temperature. Also as disclosed in patent CN201611101271.1, a method for preparing a porous ceramic-metal gradient composite membrane is provided, in which a suspension solution is prepared from a mixed powder of metal and ceramic with continuously changing particle sizes, a gradient membrane layer is deposited on the surface of a porous substrate by utilizing the difference of sedimentation velocities, and then a heat treatment and sintering are performed to obtain a formed porous ceramic-metal gradient composite membrane. The method slows down the cracking caused by different shrinkage degrees of different parts in the sintering process, but no transition layer exists between the film layer and the substrate, and metal powder with fine granularity exists in the ceramic film layer, so that the bonding strength of the sintered ceramic layer and the metal substrate is difficult to ensure, and the service life of the film layer under the cross-flow filtration working condition is difficult to ensure.
Disclosure of Invention
The invention aims to solve the problems that the existing ceramic composite membrane is easy to delaminate and crack, easy to fall off, discontinuous in coating and defective in surface after membrane forming in the using process, and provides a porous metal-based ceramic composite membrane and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
the present invention first provides a porous metal-based ceramic composite membrane comprising:
the ceramic composite layer, the metal powder transition layer and the porous metal matrix;
the metal powder transition layer is arranged between the ceramic composite layer and the porous metal matrix.
Preferably, the porous metal matrix is selected from a pore size range of 5 μm to 50 μm, and the material is selected from one of 304, 310S or 316L.
Preferably, the metal powder transition layer is a submicron metal coating with the pore diameter of 0.5-5 μm, and the material is selected from one of 304, 310S or 316L.
Preferably, the ceramic composite layer is made of raw material powder with the aperture range of 15-200nm and T iO 2 、SiO 2 Or Al 2 O 3 One kind of (1).
Preferably, the thickness of the porous metal matrix is 1-3mm, the thickness of the metal powder transition layer is less than 200 μm, and the thickness of the ceramic composite layer is 100-500nm.
The invention also provides a preparation method of the porous metal-based ceramic composite membrane, which comprises the following steps:
the method comprises the following steps: adding metal powder into a water-soluble organic additive, and uniformly stirring to obtain metal powder transition layer slurry;
step two: coating the metal powder transition layer slurry obtained in the step one on the surface of a porous metal matrix, drying, and then carrying out oxidation sintering in a vacuum sintering furnace to form a metal powder transition layer on the surface of the porous metal matrix;
step three: adding the ceramic oxide powder into a water-soluble organic additive, and uniformly stirring to obtain ceramic layer slurry;
step four: and coating the ceramic layer slurry obtained in the third step on the surface of the metal powder transition layer obtained in the second step, drying and sintering to obtain the porous metal-based ceramic composite membrane.
Preferably, in the second step, the vacuum degree of the vacuum sintering furnace is 5 × 10 -3 -9×10 -3 Pa, the oxidizing sintering temperature is 700-1000 ℃, and the time is 2-4h.
Preferably, the water-soluble organic additive in the first step and the third step comprises one or more of polyvinyl alcohol, methyl cellulose, polyethylene glycol, glycerol or dibutyl phthalate.
Preferably, the sintering temperature in the fourth step is 500-900 ℃, and the sintering time is 2-4h.
Preferably, the coating mode of the second step and the fourth step is negative pressure powdering or grouting.
The invention has the advantages of
1. Uniform and continuous film layer and less surface defects
The invention provides a porous metal-based ceramic composite membrane and a preparation method thereof, the method prepares a metal powder transition layer and ceramic layer coating slurry through a grinding and dispersing all-in-one machine, effectively solves the problem that ultrafine metal and ceramic powder are easy to agglomerate in the slurry, and prepares a final composite porous membrane layer through a sintering forming mode after a membrane layer with uniform thickness is formed through negative pressure powdering.
2. The composite layer has high bonding strength and good temperature resistance
The experiment of the invention compares the bonding strength of the metal ceramic composite film layer prepared by the method of the invention and the metal ceramic composite film layer prepared by the sol-gel method, and the indentation method tests that the metal ceramic composite film layer prepared by the method of the invention has no change under the condition that the same ballast load is applied to the film layer, but the film layer prepared by the sol-gel method has obvious abrasion and shedding. Meanwhile, the experiment compares the temperature resistance of the metal ceramic composite membrane prepared by the two methods at 400 ℃, and the continuous 2-hour temperature resistance comparison shows that the membrane layer prepared by the sol-gel method is cracked and peeled, but the membrane layer prepared by the design method of the invention is not obviously changed.
3. Has strong process universality, and is suitable for preparing composite films of substrates with different shapes and sizes and different structures
The preparation process provided by the invention is suitable for preparing the metal ceramic composite film layer on the surface of the tubular, flaky and other external metal matrixes with any size, can be suitable for local or specific surface compounding, such as an external surface or an internal surface, and has strong universality on different types of base materials.
4. Low preparation cost and long service life
The method designed by the invention adopts the traditional powder metallurgy process to prepare the product, does not need special equipment or tooling dies, has low product preparation cost and high output efficiency, and the prepared metal ceramic composite membrane filter material has good filtering performance, physical strength and environmental adaptability and longer service life.
Drawings
In order to more clearly illustrate the embodiments of the present application or technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings can be obtained by those skilled in the art according to the drawings.
Fig. 1 is a schematic structural view of a porous cermet composite membrane prepared in example 1 of the present invention.
FIG. 2 is a schematic structural diagram of a porous cermet composite membrane prepared in example 2 of the present invention.
FIG. 3 is a scanning electron micrograph of the porous cermet composite membrane prepared in example 1 of the present invention.
Description of reference numerals:
1. a ceramic composite layer; 2. a metal powder transition layer; 3. a porous metal matrix.
Detailed Description
The present invention first provides a porous metal-based ceramic composite membrane, as shown in fig. 1 and 2, comprising:
the ceramic composite layer 1, the metal powder transition layer 2 and the porous metal matrix 3;
the metal powder transition layer 2 is arranged between the ceramic composite layer 1 and the porous metal matrix 3.
According to the invention, according to the actual use requirement, the porous metal-based ceramic composite membrane can be prepared into an outer surface coating, as shown in figure 1, the porous metal-based ceramic composite membrane sequentially comprises a porous metal matrix 3, a metal powder transition layer 2 and a ceramic composite layer 1 from inside to outside; or the porous metal-based ceramic composite membrane is prepared into an inner surface coating, and as shown in figure 2, the porous metal-based ceramic composite membrane sequentially comprises a ceramic composite layer 1, a metal powder transition layer 2 and a porous metal matrix 3 from inside to outside.
The porous metal matrix 3 of the invention preferably adopts one of 304, 310S and 316L with the aperture range of 5-50 μm; the thickness of the porous metal substrate 3 is preferably 1 to 3mm; the metal powder transition layer 2 is preferably a submicron metal coating with the aperture of 0.5-5 μm, and is made of one of 304, 310S and 316L; the thickness of the metal powder transition layer 2 is preferably < 200 μm; the ceramic composite layer 1 is made of raw material powder with the aperture range of 15-200nm and the material quality of T iO 2 、S iO 2 Or A l 2 O 3 To (3) is provided. Coating the cleaned surface of the porous metal matrix 3 with slurry prepared by submicron metal powder, oxidizing the surface of the porous metal matrix in a sintering mode to form a porous metal powder transition layer 2, coating the slurry prepared by the nanoscale ceramic powder on the metal powder transition layer, and further sintering to prepare the high-bonding-strength ceramic composite layer 1 which is attached to the inner surface or the outer surface and has the thickness of about 100-500nm.
The invention also provides a preparation method of the porous metal-based ceramic composite membrane, which comprises the following steps:
the method comprises the following steps: adding metal powder into a water-soluble organic additive, and uniformly stirring to obtain metal powder transition layer slurry; the pore diameter of the metal powder is preferably 0.5-5 μm, the material is one of 304, 310S and 316L, and the water-soluble organic additive preferably comprises one or more of polyvinyl alcohol, methyl cellulose, polyethylene glycol, glycerol or dibutyl phthalate;
step two: coating the metal powder transition layer slurry obtained in the step one on the outer surface or the inner surface of the porous metal matrix, drying and then carrying out oxidation sintering in a vacuum sintering furnace, wherein the vacuum degree of the vacuum sintering furnace is preferably 5 x 10 -3 -9×10 -3 Pa, oxidizing and sintering at 700-1000 ℃ for 2-4h, and forming a metal powder transition layer on the outer surface or the inner surface of the porous metal matrix; the coating mode is not particularly limited, and the coating mode known in the art can be adopted, and the negative pressure powdering or grouting mode is preferred; because the surface energy of the submicron metal powder is relatively high, the formed film layer is more sensitive to the vacuum degree in a hearth in the sintering process, and therefore, a uniform and continuous oxidized metal powder transition layer with obvious sintering necks can be formed on the surface of the porous metal matrix by controlling the vacuum degree; the porous metal matrix 3 preferably has a pore diameter ranging from 5 μm to 50 μm and is made of one of 304L, 310S and 316L; the thickness of the porous metal matrix 3 is preferably 1-3mm, and the thickness of the metal powder transition layer 2 is preferably less than 200 μm.
Step three: adding ceramic oxide powder into a water-soluble organic additive, and uniformly stirring to obtain ceramic layer slurry; the ceramic oxide powder preferably has a particle size of 15-200nm and is made of TiO 2 、SiO 2 Or Al 2 O 3 One of (1);
step four: coating the ceramic layer slurry obtained in the third step on the outer surface or the inner surface of the metal powder transition layer obtained in the second step, drying and sintering, wherein the sintering temperature is preferably 500-900 ℃, and the sintering time is preferably 2-4h, so as to obtain the porous metal-based ceramic composite membrane. The coating method is not particularly limited, and a coating method known in the art may be adopted, and a negative pressure powdering or grouting method is preferred. The thickness of the ceramic composite layer is preferably 100-500nm.
The present invention is further illustrated by reference to the following specific examples, in which the starting materials are all commercially available.
Example 1
1. A316L stainless steel tubular porous metal matrix with the aperture of 10 mu m is selected as a matrix of the metal ceramic composite material, and absolute ethyl alcohol is used for ultrasonically removing surface impurities and oil stains for later use.
2. 1000g of 316L stainless steel powder with the median diameter of 2 mu m is added into 400ml of water-soluble organic additive, and the powder, the methylcellulose and the polyethylene glycol are uniformly stirred by a submicron grinding and dispersing all-in-one machine to form stable slurry.
3. The prepared stainless steel slurry is sprayed on the outer surface of the porous metal matrix by using a negative pressure spray gun, and the thickness of the coating is calculated to be 100 mu m according to the powder quantity.
4. Drying the surface of the coating, putting the dried coating into a vacuum sintering furnace, and controlling the vacuum degree in a hearth to be more than 5 multiplied by 10 -3 And Pa, carrying out oxidation sintering for 2h at the temperature of 900 ℃, and forming a uniformly oxidized transition film layer on the surface.
5. SiO with the median diameter of 50nm 2 50g of ceramic oxide powder is added into 400ml of water-soluble organic additive, and the powder, methylcellulose and polyethylene glycol are uniformly stirred by using a nano-grade grinding and dispersing integrated machine to form stable slurry.
6. The prepared ceramic slurry is sprayed on the surface of the oxidized metal powder transition layer of the metal matrix by using a negative pressure spray gun, and the thickness of the coating is calculated to be 200nm according to the powder loading amount.
7. And (3) drying the surface of the coating, putting the coating into an atmosphere furnace, and sintering for 2 hours at 900 ℃ under the protection of inert gas to obtain the porous ceramic membrane with uniform surface and 150nm of coating thickness. As shown in fig. 1.
Taking a ring-shaped sample of the metal ceramic composite material prepared in the example 1, testing the bonding strength of the coating at normal temperature by adopting an indentation method, applying a force with a ballast load of 150kgf on the surface of the ceramic coating, releasing the pressure after keeping for 6s, and observing the ceramic film layer on the surface under a microscope without cracking or falling off.
The metal ceramic composite material prepared in the example 1 is placed in a constant temperature oven at 400 ℃, and is taken out after 2 hours, and the ceramic film layer on the outer surface is observed not to be obviously changed.
FIG. 3 is a scanning electron microscope photograph of the porous cermet composite membrane prepared in example 1 of the present invention, and it can be seen from the photograph that the porous cermet composite membrane prepared in the present invention has uniform pores, good consistency and few surface defects.
Example 2
1. A316L stainless steel tubular porous metal matrix with the aperture of 10 mu m is selected as a matrix of the metal ceramic composite material, and absolute ethyl alcohol is used for ultrasonically removing surface impurities and oil stains for later use.
2. 1000g of 316L stainless steel powder with the median diameter of 2 mu m is added into 400ml of water-soluble organic additive, and the powder, methylcellulose and polyethylene glycol are uniformly stirred by a submicron grinding and dispersing all-in-one machine to form stable slurry.
3. And (3) adopting a special preparation tool for an inner coating, coating the uniformly prepared stainless steel slurry on the inner surface of the porous metal matrix in a grouting mode, and calculating the thickness of the coating to be 100 mu m according to the powder quantity.
4. Drying the surface of the coating, putting the dried coating into a vacuum sintering furnace, and controlling the vacuum degree in a hearth to be more than 5 multiplied by 10 -3 And Pa, carrying out oxidation sintering for 2h at the temperature of 900 ℃, and forming a uniformly oxidized transition film layer on the inner surface.
5. TiO with the median diameter of 50nm 2 Adding 50g of ceramic oxide powder into 400ml of water-soluble organic additive, and uniformly stirring the powder, methylcellulose and polyethylene glycol by using a nano-grade grinding and dispersing all-in-one machine to form stable slurry.
6. And (3) adopting a special preparation tool for an inner coating, coating the uniformly prepared ceramic powder slurry on the inner surface of the oxidized metal powder transition layer of the metal matrix in a grouting manner, and calculating the thickness of the coating to be 200nm according to the powder quantity.
7. And (3) drying the surface of the coating, putting the coating into an atmosphere furnace, and sintering for 2 hours at 1100 ℃ under the protection of hydrogen gas to obtain the porous ceramic membrane with uniform surface and 150nm of coating thickness. As shown in fig. 2.
Taking an annular sample of the metal ceramic composite material prepared in the example 2, testing the bonding strength of the coating at normal temperature by adopting an indentation method, applying a force with a ballast load of 150kgf on the surface of the ceramic coating, releasing pressure after keeping for 6s, and observing the ceramic film layer on the surface under a microscope without cracking and falling off.
The metal ceramic composite material prepared in the embodiment 2 is placed in a constant temperature oven at 400 ℃, taken out after 2 hours, and the ceramic film layer on the inner surface is observed to be not obviously changed.
Example 3
1. A316L stainless steel sheet-shaped porous metal matrix with the aperture of 8 mu m is selected as a matrix of the metal ceramic composite material, and absolute ethyl alcohol is used for ultrasonically removing surface impurities and oil stains for later use.
2. 1000g of 316L stainless steel powder with the median diameter of 2 mu m is added into 500ml of water-soluble organic additive, and the powder, methylcellulose and polyethylene glycol are uniformly stirred by a submicron grinding and dispersing all-in-one machine to form stable slurry.
3. The prepared stainless steel slurry was sprayed on the outer surface of the porous metal substrate using a negative pressure spray gun, and the coating thickness was 80 μm calculated from the amount of powder applied.
4. Drying the surface of the coating, putting the dried coating into a vacuum sintering furnace, and controlling the vacuum degree in a hearth to be more than 5 multiplied by 10 -3 And Pa, carrying out oxidation sintering for 2h at the temperature of 900 ℃, and forming a uniformly oxidized transition film layer on the surface.
5. 50g of SiO 2 ceramic oxide powder with the median diameter of 50nm is added into 400ml of water-soluble organic additive, and the powder, methylcellulose and polyethylene glycol are uniformly stirred by using a nano-grade grinding and dispersing all-in-one machine to form stable slurry.
6. The prepared ceramic slurry is sprayed on the surface of the oxidized metal powder transition layer of the metal matrix by using a negative pressure spray gun, and the thickness of the coating is calculated to be 200nm according to the powder loading amount.
7. And (3) drying the surface of the coating, putting the coating into an atmosphere furnace, and sintering for 2 hours at 900 ℃ under the protection of inert gas to obtain the porous ceramic membrane with uniform surface and 150nm of coating thickness.
8. The sintered metal ceramic composite filter element can be made into metal ceramic composite tubular membranes with different sizes and specifications by a reel pipe welding mode.
Taking a sheet sample of the metal ceramic composite material prepared in the embodiment 3, testing the bonding strength of the coating at normal temperature by adopting an indentation method, applying a force with a ballast load of 150kgf on the surface of the ceramic coating, releasing the pressure after keeping for 6s, and observing the ceramic film layer on the surface under a microscope without cracking or falling off.
The metal ceramic composite material prepared in the embodiment 3 is placed in a constant temperature oven at 400 ℃, and is taken out after 2 hours, and the surface ceramic film layer is observed to be not obviously changed.
Comparative example 1
1. A316L stainless steel tubular porous metal matrix with the aperture of 10 mu m is selected as a matrix of the metal ceramic composite material, and absolute ethyl alcohol is used for ultrasonically removing surface impurities and oil stains for later use.
2. 1000g of 316L stainless steel powder with the median diameter of 2 mu m is added into 400ml of water-soluble organic additive, and the powder, methylcellulose and polyethylene glycol are uniformly stirred by a submicron grinding and dispersing all-in-one machine to form stable slurry.
3. The prepared stainless steel slurry was sprayed on the outer surface of the porous metal substrate using a negative pressure spray gun, and the coating thickness was calculated to be 100 μm according to the amount of powder applied.
4. After the surface of the coating is dried, the coating is put into a vacuum sintering furnace, and the vacuum degree in a hearth is controlled to be less than 5 multiplied by 10 -3 And Pa, carrying out oxidation sintering for 2h at the temperature of 900 ℃, and forming a uniform microporous metal transition film layer on the surface.
5. SiO with the median diameter of 50nm 2 Adding 50g of ceramic oxide powder into 400ml of water-soluble organic additive, and uniformly stirring the powder, methylcellulose and polyethylene glycol by using a nano-grade grinding and dispersing all-in-one machine to form stable slurry.
6. And spraying the prepared ceramic slurry on the surface of the transition layer of the oxidized metal powder of the metal matrix by using a negative pressure spray gun, and calculating the thickness of the coating to be 200nm according to the powder quantity.
7. And drying the surface of the coating, putting the coating into an atmosphere furnace, and sintering for 2 hours at 900 ℃ under the protection of inert gas to obtain the porous ceramic composite membrane with the thickness of 150 nm.
The surface of the sintered metal ceramic composite sample coating of the comparative example 1 has obvious cracks, a continuous sintering neck is not formed between the sintered metal ceramic composite sample coating and a matrix, and the sintered metal transition layer cannot react and fuse with ceramic particles and has poor bonding strength with the matrix.
Comparative example 2
1. A316L stainless steel tubular porous metal matrix with the aperture of 10 mu m is selected as a matrix of the metal ceramic composite material, and absolute ethyl alcohol is used for ultrasonically removing surface impurities and oil stains for later use.
2. 1000g of 316L stainless steel powder with the median diameter of 2 mu m is added into 400ml of water-soluble organic additive, and the powder, the methylcellulose and the polyethylene glycol are uniformly stirred by a submicron grinding and dispersing all-in-one machine to form stable slurry.
3. And (3) adopting a special preparation tool for an inner coating, coating the uniformly prepared stainless steel slurry on the inner surface of the porous metal matrix in a grouting mode, and calculating the thickness of the coating to be 100 mu m according to the powder quantity.
4. Drying the surface of the coating, putting the dried coating into a vacuum sintering furnace, and controlling the vacuum degree in a hearth to be more than 5 multiplied by 10 -3 And Pa, carrying out oxidation sintering for 2h at the temperature of 900 ℃, and forming a uniformly oxidized transition film layer on the inner surface.
5. High-concentration silica sol with the median diameter of 20nm and the model of JN-40 is uniformly stirred with methylcellulose and polyethylene glycol to form stable slurry.
6. And (3) adopting a self-made special preparation tool for the inner coating, coating the uniformly prepared slurry on the surface of the oxidized metal powder transition layer of the metal matrix in a grouting mode, and calculating the thickness of the coating to be 200nm according to the powder coating amount.
7. After the surface of the coating is dried, the coating is put into an oven and slowly heated to 280 ℃ at the speed of 2 ℃/min to dry and solidify the ceramic coating, and the porous ceramic membrane with uniform surface and 150nm of coating thickness is obtained.
Taking an annular sample of the metal ceramic composite material prepared in the comparative example 2, testing the bonding strength of the coating at normal temperature by adopting an indentation method, applying a force with a ballast load of 150kgf on the surface of the ceramic coating, and keeping the pressure relief after 6s, so that the ceramic film on the surface has cracks and falls off.
And (3) placing the metal ceramic composite material prepared in the comparative example 2 in a constant-temperature oven at 400 ℃, taking out after 2h, and observing that the ceramic film layer on the surface is cracked and peeled from the substrate, so that the coating is peeled off.
Claims (10)
1. A porous metal-based ceramic composite membrane, comprising:
the ceramic composite layer (1), the metal powder transition layer (2) and the porous metal matrix (3);
the metal powder transition layer (2) is arranged between the ceramic composite layer (1) and the porous metal matrix (3).
2. The porous cermet based ceramic composite membrane according to claim 1, wherein the porous metal substrate (3) is selected from one of 304, 310S or 316L with a pore size ranging from 5 μm to 50 μm.
3. The porous metal-based ceramic composite membrane according to claim 1, wherein the metal powder transition layer (2) is a submicron metal coating with a pore size of 0.5-5 μm, and is made of one of 304, 310S or 316L.
4. The porous metal-based ceramic composite membrane according to claim 1, wherein the ceramic composite membrane (1) is made of TiO, and the pore size of the raw material powder is in the range of 15-200nm 2 、SiO 2 Or Al 2 O 3 One kind of (1).
5. The porous metal-based ceramic composite membrane according to claim 1, wherein the thickness of the porous metal substrate (3) is 1-3mm, the thickness of the metal powder transition layer (2) is less than 200 μm, and the thickness of the ceramic composite layer (1) is 100-500nm.
6. The method of preparing a porous cermet based composite membrane according to claim 1, comprising:
the method comprises the following steps: adding metal powder into a water-soluble organic additive, and uniformly stirring to obtain metal powder transition layer slurry;
step two: coating the metal powder transition layer slurry obtained in the step one on the surface of a porous metal matrix, drying, and then carrying out oxidation sintering in a vacuum sintering furnace to form a metal powder transition layer on the surface of the porous metal matrix;
step three: adding ceramic oxide powder into a water-soluble organic additive, and uniformly stirring to obtain ceramic layer slurry;
step four: and coating the ceramic layer slurry obtained in the third step on the surface of the metal powder transition layer obtained in the second step, drying and sintering to obtain the porous metal-based ceramic composite membrane.
7. The method for preparing a porous cermet substrate composite membrane according to claim 6, wherein in the second step, the vacuum degree of the vacuum sintering furnace is 5 x 10 -3 -9×10 -3 Pa, the oxidizing sintering temperature is 700-1200 ℃, and the time is 2-4h.
8. The method for preparing a porous cermet composite membrane according to claim 6, wherein the water-soluble organic additive of step one and step three includes one or more of polyvinyl alcohol, methyl cellulose, polyethylene glycol, glycerol or dibutyl phthalate.
9. The method for preparing a porous metal-based ceramic composite membrane according to claim 6, wherein the sintering temperature in the fourth step is 900-1100 ℃ and the sintering time is 2-4h.
10. The method for preparing a porous cermet substrate composite membrane according to claim 6, wherein the coating method of the second and fourth steps is negative pressure powdering or grouting.
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